CN116751360B - Polyester resin and preparation method thereof - Google Patents
Polyester resin and preparation method thereof Download PDFInfo
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- CN116751360B CN116751360B CN202311048020.1A CN202311048020A CN116751360B CN 116751360 B CN116751360 B CN 116751360B CN 202311048020 A CN202311048020 A CN 202311048020A CN 116751360 B CN116751360 B CN 116751360B
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- acid
- polyester resin
- flame
- retardant
- heating
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 86
- 239000004645 polyester resin Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000003063 flame retardant Substances 0.000 claims abstract description 81
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 79
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002253 acid Substances 0.000 claims abstract description 46
- 239000002904 solvent Substances 0.000 claims abstract description 26
- -1 dithio diol Chemical class 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- KWZKULZCUKLHRG-UHFFFAOYSA-N (carboxydisulfanyl)formic acid Chemical compound OC(=O)SSC(O)=O KWZKULZCUKLHRG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 57
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 46
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 46
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 39
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 37
- 239000011976 maleic acid Substances 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 37
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 23
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 229960004063 propylene glycol Drugs 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 12
- YCLSOMLVSHPPFV-UHFFFAOYSA-N 3-(2-carboxyethyldisulfanyl)propanoic acid Chemical compound OC(=O)CCSSCCC(O)=O YCLSOMLVSHPPFV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 9
- 235000013772 propylene glycol Nutrition 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical group CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 8
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 5
- RXURJOBHVPLGQU-UHFFFAOYSA-N 3-(3-hydroxypropyldisulfanyl)propan-1-ol Chemical compound OCCCSSCCCO RXURJOBHVPLGQU-UHFFFAOYSA-N 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- MWSXXXZZOZFTPR-OWOJBTEDSA-N (e)-hex-3-ene-1,6-diol Chemical compound OCC\C=C\CCO MWSXXXZZOZFTPR-OWOJBTEDSA-N 0.000 claims description 3
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 claims description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- IPOOKKJSFZYCSH-OWOJBTEDSA-N (e)-oct-4-ene-1,8-diol Chemical compound OCCC\C=C\CCCO IPOOKKJSFZYCSH-OWOJBTEDSA-N 0.000 claims description 2
- KAPUPNHDWNOREH-UHFFFAOYSA-N 3-(1-hydroxyhexan-3-yldisulfanyl)hexan-1-ol Chemical compound CCCC(CCO)SSC(CCC)CCO KAPUPNHDWNOREH-UHFFFAOYSA-N 0.000 claims description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229940117969 neopentyl glycol Drugs 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 3
- 150000002009 diols Chemical class 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 24
- 238000012360 testing method Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 230000006872 improvement Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 238000004064 recycling Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BPZIYBJCZRUDEG-UHFFFAOYSA-N 2-[3-(1-hydroxy-2-methylpropan-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropan-1-ol Chemical compound C1OC(C(C)(CO)C)OCC21COC(C(C)(C)CO)OC2 BPZIYBJCZRUDEG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229960002479 isosorbide Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6928—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a polyester resin and a preparation method thereof, belonging to the technical field of high polymer materials. The polyester resin is formed by dibasic acid, flame-retardant acid and/or flame-retardant alcohol, dithio diol and/or dithio dicarboxylic acid and diol components, and modified nano silicon dioxide is added. The polyester resin prepared by the invention has good flame retardance, heat resistance, solvent resistance, corrosion resistance and ageing resistance, good mechanical property, degradability, recovery and self-healing property, wide raw material sources and low cost, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to polyester resin and a preparation method thereof.
Background
Aromatic saturated polyester resins, particularly polyethylene terephthalate (hereinafter also referred to as "PET"), are resins that are balanced in mechanical properties, solvent resistance, fragrance retention, weather resistance, recyclability, and the like, and are used in a large number of applications such as bottles and films. However, PET has drawbacks with respect to crystallinity and heat resistance. That is, since PET has high crystallinity, if a molded article or sheet having a thickness is to be produced, whitening occurs due to crystallization, which may deteriorate transparency. In addition, since the glass transition temperature of PET is about 80 ℃, the heat resistance is poor. Meanwhile, the polyester resin is mainly composed of carbon element and hydrogen element, has low Limiting Oxygen Index (LOI), is extremely easy to burn, has poor flame retardant property and heat resistance, generates a large amount of harmful dense smoke during burning, and has poor carbon forming capability. And such polyester resins are inferior in degradability and mechanical properties.
In order to produce a polyester resin excellent in heat resistance, transparency and mechanical properties, patent document 1 discloses a polyester resin obtained by copolymerizing 3, 9-bis (1, 1-dimethyl-2-hydroxyethyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane (hereinafter also referred to as "spiro glycol") with a dicarboxylic acid component. Patent document 2 discloses a process for producing a spiroglycol having such a thermal stability that it is not easily decomposed when heated.
Patent document 3 discloses a polyester resin which uses isosorbide as a biomass-derived monomer and has excellent heat resistance used in the fields of fibers, films and the like.
Patent document 5 discloses a technique for improving storage stability and grindability at high temperature by using anhydroerythritol as a polyester resin for toner binder.
However, these raw materials are complicated in treatment or preparation process, low in yield, and the produced polyester resin is poor in flame retardance, mechanical properties and aging resistance.
Patent literature:
patent document 1: japanese patent laid-open No. 2002-69165;
patent document 2: japanese patent laid-open publication No. 2005-187425;
patent document 3: japanese patent application laid-open No. 2006-511688;
patent document 4: japanese patent laid-open No. 2008-239744;
patent document 5: japanese patent application laid-open No. 2013-256599.
Disclosure of Invention
The invention aims to provide a polyester resin and a preparation method thereof, which have the advantages of good flame retardance, heat resistance, solvent resistance, corrosion resistance, ageing resistance, good mechanical property, degradability, recovery and self-healing property, wide raw material sources, low cost and wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a polyester resin, which is formed by dibasic acid, flame-retardant acid and/or flame-retardant alcohol, dithio diol and/or dithio dicarboxylic acid and diol components, and modified nano silicon dioxide is added;
the structural formula of the flame retardant acid is shown as formula I:
a formula I;
the structural formula of the flame-retardant alcohol is shown as formula II:
a formula II;
wherein r=c0-C3 alkyl chain;
the modified nano silicon dioxide is KH560 modified nano silicon dioxide particles.
As a further improvement of the invention, the dibasic acid is at least one selected from itaconic acid, maleic acid, isophthalic acid and succinic acid, preferably is a mixture of itaconic acid and maleic acid, and the molar ratio is 10-12:3-5; the dithioglycol is at least one selected from 3,3 '-dithiobis (propane-1-ol) and 3,3' -dithiobis (hexane-1-ol); the dithiodicarboxylic acid is 3,3' -dithiodipropionic acid; the dihydric alcohol is at least one selected from ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol and neopentyl glycol.
As a further improvement of the invention, the flame retardant is formed by itaconic acid, maleic acid, flame retardant acid, 3' -dithiobis (propane-1-ol) and 1, 2-propylene glycol, wherein the molar ratio is 10-12:3-5:0.5-1:1-2:11.5-16.
As a further improvement of the invention, the flame-retardant polyurethane foam is formed by itaconic acid, maleic acid, flame-retardant alcohol, 3' -dithiodipropionic acid and ethylene glycol, wherein the molar ratio is 10-12:3-5:0.7-1.2:0.9-1.5:13.2-17.3.
As a further improvement of the present invention, the preparation method of the flame retardant acid is as follows: dissolving 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid in a solvent, heating and stirring for reaction under the protection of inert gas, filtering, washing and drying to obtain the flame-retardant acid.
As a further improvement of the invention, the mol ratio of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the itaconic acid is 1:1-1.05, the solvent is at least one of toluene, xylene and tetrahydrofuran, the temperature of the heating and stirring reaction is 100-110 ℃, and the time is 7-10h.
As a further improvement of the present invention, the preparation method of the flame-retardant alcohol is as follows: dissolving 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dihydric alcohol in a solvent, heating and stirring for reaction under the protection of inert gas, filtering, washing and drying to obtain the flame-retardant alcohol.
As a further improvement of the invention, the mol ratio of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the dihydric alcohol is 1:1.1-1.2, the dihydric alcohol is at least one selected from 1-ethylene-1, 2-diol, 2-butene-1, 4-diol, 3-hexene-1, 6-diol and 4-octene-1, 8-diol, the solvent is at least one selected from toluene, xylene, tetrahydrofuran and ethyl acetate, the temperature of the heating and stirring reaction is 90-100 ℃ and the time is 6-8h.
The invention further provides a preparation method of the polyester resin, which comprises the following steps:
s1, uniformly mixing dibasic acid, flame-retardant acid and/or flame-retardant alcohol, dithioglycol and/or dithiodicarboxylic acid, dihydric alcohol, polymerization inhibitor and catalyst, heating and stirring for reaction, stopping heating when the acid value is reduced to 45-50mgKOH/g, cooling to room temperature, adding dichloromethane for dissolution, standing, and removing the solvent under reduced pressure to obtain a prepolymer;
s2, adding the alkyl orthosilicate into ethanol, adding KH560, water and ammonia water, heating, stirring and mixing for reaction to form sol, and obtaining modified silica sol;
s3, adding the prepolymer prepared in the step S1 and the modified silica sol prepared in the step S2 into a diluent, adding an initiator, stirring and mixing uniformly, and reacting and curing to obtain the polyester resin.
As a further improvement of the invention, the polymerization inhibitor is hydroquinone, the addition amount is 0.5-1wt% of the total mass of the system, the catalyst is p-toluenesulfonic acid or cobalt isooctanoate, the addition amount is 0.01-0.02wt% of the total mass of the system, the initiator is 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide or methyl ethyl ketone peroxide, the mass ratio of the modified silica sol to the prepolymer to the diluent is 3-5:15-20:10-20:0.01-0.02, the curing condition is ultraviolet light curing for 10-15min or heating to 50-60 ℃ for curing for 1-2h, the mass ratio of the alkyl orthosilicate, ethanol, KH560, water to ammonia water is 12-15:30-50:3-5:15-20:7-10, the concentration of the ammonia water is 22-25wt%, and the alkyl orthosilicate is methyl orthosilicate or ethyl orthosilicate.
Preferably, the diluent is selected from at least one of acetone, methanol, ethanol, butanone and tetrahydrofuran.
The invention has the following beneficial effects:
the 9, 10-diammine-9-oxa-10- phenanthrene-10-oxide (DOPO) and derivatives thereof have higher thermal stability, and can be used for preparing a reactive flame retardant, so that the flame retardant and the heat resistance of the polyester resin are improved by adding the reactive flame retardant into the synthesis of the polyester resin. According to the invention, the DOPO is reacted with the bio-based material itaconic acid to prepare the flame-retardant acid, so that the phosphorus content in the polyester resin is improved in the molecular formation of the polyester resin, the flame-retardant modified and heat-resistant modified effects are good, and the mechanical properties of the polyester resin are improved in the presence of the itaconic acid. In addition, the DOPO and the alkene glycol react to obtain a plurality of flame-retardant alcohols, the structure of the polyester resin is enriched, and the prepared polyester resin has good flame retardance and heat resistance. The preparation method of the flame-retardant acid and the flame-retardant alcohol is simple, the yield is high, and the synthesis conditions are mild.
The itaconic acid can be prepared by fermenting agriculture and forestry biomass such as lignocellulose through microorganisms, has wide raw material sources and low cost, contains conjugated double bonds and carboxyl groups in the molecule, has very active chemical properties, can be used as one of the reaction raw materials of the polyester resin, and has low viscosity and low volatility, so that the preparation process of the polyester resin is simpler and more convenient. In addition, the maleic acid is also a bio-based source diacid, and by introducing itaconic acid and maleic acid as the diacid, the mechanical property, solvent resistance and thermal stability of the polyester resin are obviously improved, the preparation cost is lower, and the polyester resin can be recycled.
According to the invention, the disulfide diol and the disulfide dicarboxylic acid are introduced, so that the disulfide compound can be used as a reaction raw material of the polyester resin, on the other hand, disulfide bonds of the disulfide compound have reversible covalent bonds, and the disulfide bonds can be broken and recombined when the disulfide compound is stimulated by the outside, so that the prepared polyester resin has the performances of repeated processing, recycling and the like, the environment friendliness of the polyester resin is greatly improved, the material is placed in a hot organic solution for soaking, the material can be completely dissolved, the recycling of the material is realized, meanwhile, the disulfide bond can be uniformly decomposed under the irradiation of common lamplight, and the repair of cracks of the polyester resin material is realized.
In the preparation process of the polyester resin, KH560 modified silica particles are also added, and the modified silica particles are introduced, so that epoxy groups carried by the modified silica particles can participate in the synthesis of the resin due to the modification of KH560, so that inorganic particles are uniformly dispersed in the polyester resin, the dispersibility of inorganic materials is improved, and the mechanical property, high temperature resistance, corrosion resistance and ageing resistance of the polyester resin are greatly improved through the modification of the KH560 modified silica particles.
The polyester resin prepared by the invention has good flame retardance, heat resistance, solvent resistance, corrosion resistance and ageing resistance, good mechanical property, degradability, recovery and self-healing property, wide raw material sources and low cost, and has wide application prospect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Preparation example 1 preparation of flame retardant acid
The synthetic route is as follows:
；
the method comprises the following steps: 0.1mol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 0.102mol of itaconic acid are dissolved in 200mL of mixed solvent (mixed solvent of dimethylbenzene and tetrahydrofuran, volume ratio is 5:1), heated to 105 ℃ under the protection of nitrogen, stirred and reacted for 8 hours, filtered, washed by tetrahydrofuran and dried to prepare the flame-retardant acid. ESI-MS calculated: c (C) 17 H 16 O 6 P (m+h) + 347.07, found: 347.1, yield of94.5%。
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ11.0（br，2H），7.5（d，1H），7.3-7.31（m，3H），7.2（m，1H），7.05（m，1H），6.88（m，1H），6.78（d，1H），2.7（t，1H），2.46（d，2H），1.6（d，2H）。
preparation example 2 preparation of flame retardant alcohol
The synthetic route is as follows:
；
the method comprises the following steps: 0.1mol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 0.11mol of 1-ethylene-1, 2-diol are dissolved in 200mL of mixed solvent (mixed solvent of toluene and ethyl acetate with the volume ratio of 3:1), heated to 90 ℃ under the protection of nitrogen, stirred and reacted for 6 hours, filtered, washed by ethyl acetate and dried to prepare the flame-retardant alcohol. ESI-MS calculated: c (C) 14 H 14 O 4 P (m+h) + 277.06, found: 277.1, yield 95.2%.
Nuclear magnetic results:
1 H NMR(300MHz，CDCl 3 )δ7.50（d，1H），7.22-7.31（m，4H），7.05（m，1H），6.79-6.82（m，2H），3.7（t，2H），3.3（t，1H），2.0（br，2H）。
preparation example 3 preparation of flame retardant alcohol
The synthetic route is as follows:
；
the method comprises the following steps: dissolving 0.1mol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 0.12mol of 2-butene-1, 4-diol in 200mL of mixed solvent (mixed solvent of toluene and ethyl acetate with the volume ratio of 3:1), heating to 100 ℃ under the protection of nitrogen, stirring and reacting for 8 hours, filtering, washing with ethyl acetate, and drying to obtain the flame-retardant alcohol. ESI-MS calculated: c (C) 16 H 18 O 4 P (m+h) + 305.09, found: 305.1, the yield was 94.7%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ7.52（d，1H），7.24-7.32（m，4H），7.07（m，1H），6.80-6.82（m，2H），3.50-3.53（m，4H），2.0（br，2H），1.62（m，1H），1.51（m，2H）。
preparation example 4 preparation of flame retardant alcohol
The synthetic route is as follows:
；
the method comprises the following steps: 0.1mol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 0.115mol of 3-hexene-1, 6-diol are dissolved in 200mL of mixed solvent (mixed solvent of toluene and ethyl acetate with the volume ratio of 3:1), and the mixture is heated to 95 ℃ under the protection of nitrogen, stirred and reacted for 7 hours, filtered, washed by ethyl acetate and dried to prepare the flame-retardant alcohol. ESI-MS calculated: c (C) 18 H 22 O 4 P (m+h) + 332.12, found: 332.1, yield 94.0%.
Nuclear magnetic results: 1 H NMR(300MHz，CDCl 3 )δ7.51（d，1H），7.25-7.32（m，4H），7.06（m，1H），6.81-6.84（m，2H），2.0（br，2H），3.51-3.53（m，4H），1.48-1.50（m，5H），1.30（m，2H）。
example 1
The embodiment provides a method for preparing polyester resin, which comprises the following steps:
s1, uniformly mixing itaconic acid, maleic acid, flame retardant acid prepared in preparation example 1, 3' -dithiobis (propane-1-ol), 1, 2-propylene glycol, a polymerization inhibitor and a catalyst, heating to 150 ℃ for stirring reaction, stopping heating when the acid value is reduced to 45mgKOH/g, cooling to room temperature, adding an equal volume of dichloromethane for dissolution, standing for 1h, and removing the solvent under reduced pressure to prepare a prepolymer;
itaconic acid, maleic acid, flame retardant acid, 3' -dithiobis (propane-1-ol), 1, 2-propanediol in a molar ratio of 10:3:0.5:1:11.5;
the polymerization inhibitor is hydroquinone, the addition amount is 0.5wt% of the total mass of the system, the catalyst is p-toluenesulfonic acid, and the addition amount is 0.01wt% of the total mass of the system;
s2, adding 12 parts by weight of tetraethoxysilane into 30 parts by weight of ethanol, adding 3 parts by weight of KH560, 15 parts by weight of water and 7 parts by weight of 22wt% ammonia water, heating to 80 ℃, and stirring and mixing for reaction for 4 hours to form sol, so as to obtain modified silica sol;
s3, adding the prepolymer prepared in the step S1 and 30 parts by weight of the modified silica sol prepared in the step S2 into 100 parts by weight of acetone, adding 0.1 part by weight of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, stirring and mixing for 10min, and curing with 400W ultraviolet light for 10min to prepare the polyester resin.
And (3) carrying out infrared spectrogram analysis: carboxyl peak (about 3100-3200 cm) -1 ) And hydroxyl peak (about 3350-3400 cm) -1 ) Almost completely disappear at 1710cm -1 And 1142cm -1 The stretching vibration peak of the ester group C=O and ether bond C-O-C appears, 1635cm -1 Absorption peak of double bond c=c, 507cm -1 And 742cm -1 The absorption peaks for S-S and C-S, it was found that the polyester resin was successfully synthesized.
Example 2
The embodiment provides a method for preparing polyester resin, which comprises the following steps:
s1, uniformly mixing itaconic acid, maleic acid, flame retardant acid prepared in preparation example 1, 3' -dithiobis (propane-1-ol), 1, 2-propylene glycol, a polymerization inhibitor and a catalyst, heating to 160 ℃ for stirring reaction, stopping heating when the acid value is reduced to 50mgKOH/g, cooling to room temperature, adding an equal volume of dichloromethane for dissolution, standing for 1h, and removing the solvent under reduced pressure to prepare a prepolymer;
itaconic acid, maleic acid, flame retardant acid, 3' -dithiobis (propane-1-ol), 1, 2-propanediol in a molar ratio of 12:5:1:2:16;
the polymerization inhibitor is hydroquinone, the addition amount is 1wt% of the total mass of the system, the catalyst is cobalt iso-octoate, and the addition amount is 0.02wt% of the total mass of the system;
s2, adding 15 parts by weight of ethyl orthosilicate into 50 parts by weight of ethanol, adding 5 parts by weight of KH560, 20 parts by weight of water and 10 parts by weight of 25wt% ammonia water, heating to 80 ℃, and stirring and mixing for reaction for 4 hours to form sol, so as to obtain modified silica sol;
s3, adding the prepolymer prepared in the step S1 and 50 parts by weight of the modified silica sol prepared in the step S2 into 200 parts by weight of butanone, adding 0.2 part by weight of methyl ethyl ketone peroxide, stirring and mixing for 10min, and heating to 55 ℃ for curing for 2h to prepare the polyester resin.
Example 3
The embodiment provides a method for preparing polyester resin, which comprises the following steps:
s1, uniformly mixing itaconic acid, maleic acid, flame retardant acid prepared in preparation example 1, 3' -dithiobis (propane-1-ol), 1, 2-propylene glycol, a polymerization inhibitor and a catalyst, heating to 155 ℃ for stirring reaction, stopping heating when the acid value is reduced to 47mgKOH/g, cooling to room temperature, adding an equal volume of dichloromethane for dissolution, standing for 1h, and removing the solvent under reduced pressure to prepare a prepolymer;
itaconic acid, maleic acid, flame retardant acid, 3' -dithiobis (propane-1-ol), 1, 2-propanediol in a molar ratio of 11:4:0.7:1.5:14.2;
the polymerization inhibitor is hydroquinone, the addition amount is 0.7wt% of the total mass of the system, the catalyst is p-toluenesulfonic acid, and the addition amount is 0.015wt% of the total mass of the system;
s2, adding 13.5 parts by weight of methyl orthosilicate into 40 parts by weight of ethanol, adding 4 parts by weight of KH560, 17 parts by weight of water and 8.5 parts by weight of 23.5wt% ammonia water, heating to 80 ℃, stirring and mixing for reaction for 4 hours to form sol, and obtaining modified silica sol;
s3, adding 170 parts of the prepolymer prepared in the step S1 and 40 parts by weight of the modified silica sol prepared in the step S2 into 150 parts by weight of tetrahydrofuran, adding 0.15 part by weight of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, stirring and mixing for 10 minutes, and curing with 400W ultraviolet light for 12 minutes to prepare the polyester resin.
Example 4
The embodiment provides a method for preparing polyester resin, which comprises the following steps:
s1, uniformly mixing itaconic acid, maleic acid, flame retardant alcohol prepared in preparation example 2, 3' -dithiodipropionic acid, ethylene glycol, a polymerization inhibitor and a catalyst, heating to 150 ℃, stirring for reaction, stopping heating when the acid value is reduced to 45mgKOH/g, cooling to room temperature, adding an equal volume of dichloromethane for dissolution, standing for 1h, and removing the solvent under reduced pressure to prepare a prepolymer;
itaconic acid, maleic acid, flame retardant alcohol, 3' -dithiodipropionic acid, ethylene glycol in a molar ratio of 10:3:0.7:0.9:13.2;
the polymerization inhibitor is hydroquinone, the addition amount is 0.5wt% of the total mass of the system, the catalyst is cobalt iso-octoate, and the addition amount is 0.01wt% of the total mass of the system;
s2, adding 15 parts by weight of methyl orthosilicate into 30 parts by weight of ethanol, adding 3 parts by weight of KH560, 15 parts by weight of water and 7 parts by weight of 22wt% ammonia water, heating to 80 ℃, and stirring and mixing for reaction for 4 hours to form sol, so as to obtain modified silica sol;
s3, adding 150 parts by weight of the prepolymer prepared in the step S1 and 30 parts by weight of the modified silica sol prepared in the step S2 into 100 parts by weight of tetrahydrofuran, adding 0.1 part by weight of methyl ethyl ketone peroxide, stirring and mixing for 10min, and heating to 60 ℃ for curing for 2h to prepare the polyester resin.
Example 5
The embodiment provides a method for preparing polyester resin, which comprises the following steps:
s1, uniformly mixing itaconic acid, maleic acid, flame retardant alcohol prepared in preparation example 3,3' -dithiodipropionic acid, ethylene glycol, a polymerization inhibitor and a catalyst, heating to 160 ℃, stirring for reaction, stopping heating when the acid value is reduced to 50mgKOH/g, cooling to room temperature, adding an equal volume of dichloromethane for dissolution, standing for 1h, and removing the solvent under reduced pressure to prepare a prepolymer;
itaconic acid, maleic acid, flame retardant alcohol, 3' -dithiodipropionic acid, ethylene glycol in a molar ratio of 12:5:1.2:1.5:17.3;
the polymerization inhibitor is hydroquinone, the addition amount is 1wt% of the total mass of the system, the catalyst is cobalt iso-octoate, and the addition amount is 0.02wt% of the total mass of the system;
s2, adding 15 parts by weight of ethyl orthosilicate into 50 parts by weight of ethanol, adding 5 parts by weight of KH560, 20 parts by weight of water and 10 parts by weight of 25wt% ammonia water, heating to 80 ℃, and stirring and mixing for reaction for 4 hours to form sol, so as to obtain modified silica sol;
s3, adding the prepolymer prepared in the step S1 of 200 and 50 parts by weight of the modified silica sol prepared in the step S2 into 200 parts by weight of a diluent, adding 0.2 part by weight of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, stirring and mixing for 10min, and performing 400W ultraviolet curing for 15min.
Example 6
The embodiment provides a method for preparing polyester resin, which comprises the following steps:
s1, uniformly mixing itaconic acid, maleic acid, flame retardant alcohol prepared in preparation example 4, 3' -dithiodipropionic acid, ethylene glycol, a polymerization inhibitor and a catalyst, heating to 155 ℃, stirring for reaction, stopping heating when the acid value is reduced to 47mgKOH/g, cooling to room temperature, adding an equal volume of dichloromethane for dissolution, standing for 1h, and removing the solvent under reduced pressure to prepare a prepolymer;
itaconic acid, maleic acid, flame retardant alcohol, 3' -dithiodipropionic acid, ethylene glycol in a molar ratio of 11:4:1:1.2:15.2;
the polymerization inhibitor is hydroquinone, the addition amount is 0.5wt% of the total mass of the system, the catalyst is p-toluenesulfonic acid, and the addition amount is 0.01wt% of the total mass of the system;
s2, adding 13.5 parts by weight of ethyl orthosilicate into 40 parts by weight of ethanol, adding 4 parts by weight of KH560, 17 parts by weight of water and 8.5 parts by weight of 23.5wt% ammonia water, heating to 80 ℃, stirring and mixing for reaction for 4 hours to form sol, and obtaining modified silica sol;
s3, adding 150 parts by weight of the prepolymer prepared in the step S1 and 40 parts by weight of the modified silica sol prepared in the step S2 into 150 parts by weight of acetone, adding 0.15 part by weight of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, stirring and mixing for 10min, and curing with 400W ultraviolet light for 10min to prepare the polyester resin.
Example 7
In comparison with example 3, there was no itaconic acid added.
The molar ratio of maleic acid, flame retardant acid, 3' -dithiobis (propane-1-ol) and 1, 2-propanediol is 15:0.7:1.5:14.2.
Example 8
In comparison with example 3, the difference is that maleic acid was not added.
The molar ratio of itaconic acid, flame retardant acid, 3' -dithiobis (propane-1-ol) and 1, 2-propanediol is 15:0.7:1.5:14.2.
Example 9
In comparison with example 6, there was no itaconic acid added.
The molar ratio of maleic acid, flame retardant alcohol, 3' -dithiodipropionic acid and ethylene glycol is 15:1:1.2:15.2.
Example 10
In comparison with example 6, the difference is that maleic acid was not added.
The mole ratio of itaconic acid, flame retardant alcohol, 3' -dithiodipropionic acid and ethylene glycol is 15:1:1.2:15.2.
Comparative example 1
The difference compared to example 3 is that no flame retardant acid was added.
The molar ratio of itaconic acid, maleic acid, 3' -dithiobis (propane-1-ol) and 1, 2-propanediol is 11:4.7:1.5:14.2.
Comparative example 2
In comparison with example 3, the difference is that 3,3' -dithiobis (propan-1-ol) was not added.
The molar ratio of itaconic acid, maleic acid, flame retardant acid and 1, 2-propanediol is 11:4:0.7:15.7.
Comparative example 3
In comparison with example 3, there was no addition of itaconic acid and maleic acid.
The molar ratio of the flame retardant acid, the 3,3' -dithiobis (propane-1-ol) and the 1, 2-propanediol is 15.7:1.5:14.2.
Comparative example 4
The difference from example 3 is that KH560 is not added in step S2.
The method comprises the following steps:
s2, adding 13.5 parts by weight of methyl orthosilicate into 40 parts by weight of ethanol, adding 17 parts by weight of water and 8.5 parts by weight of 23.5wt% ammonia water, heating to 80 ℃, stirring and mixing for reaction for 4 hours to form a sol, and obtaining the silica sol.
Comparative example 5
The difference from example 3 is that no modified silica sol was added in step S3.
The method comprises the following steps:
s3, adding the prepolymer prepared in the step S1 into 150 parts by weight of tetrahydrofuran, adding 0.15 part by weight of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, stirring and mixing for 10min, and performing 400W ultraviolet light curing for 12min to obtain the polyester resin.
Comparative example 6
The difference compared to example 6 is that no flame retardant alcohol is added.
The molar ratio of itaconic acid, maleic acid, 3' -dithiodipropionic acid and ethylene glycol is 11:4:1.2:16.2.
Comparative example 7
In comparison with example 6, the difference is that 3,3' -dithiodipropionic acid was not added.
The molar ratio of itaconic acid, maleic acid, flame retardant alcohol and ethylene glycol is 11:5.2:1:15.2.
Comparative example 8
In comparison with example 6, there was no addition of itaconic acid and maleic acid.
The mole ratio of the flame retardant alcohol to the 3,3' -dithiodipropionic acid to the ethylene glycol is 1:16.2:15.2.
Comparative example 9
The difference from example 6 is that KH560 is not added in step S2.
The method comprises the following steps:
s2, adding 13.5 parts by weight of ethyl orthosilicate into 40 parts by weight of ethanol, adding 17 parts by weight of water and 8.5 parts by weight of 23.5wt% ammonia water, heating to 80 ℃, stirring and mixing for reaction for 4 hours to form a sol, and obtaining the silica sol.
Comparative example 10
The difference from example 6 is that no modified silica sol was added in step S3.
The method comprises the following steps:
s3, adding the prepolymer prepared in the step S1 into 150 parts by weight of acetone, adding 0.15 part by weight of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, stirring and mixing for 10min, and performing 400W ultraviolet light curing for 10min to prepare the polyester resin.
Test example 1
The polyester resins prepared in examples 1 to 10 of the present invention and comparative examples 1 to 10 were subjected to mechanical property test.
The mechanical properties were measured using a universal tensile tester with a load of 5 kN. The test conditions were 25℃and the stretching rate was 5mm/min, and the spline dimensions were 80 mm X10 mm X1 mm.
The results are shown in Table 1.
TABLE 1
As shown in the table above, the polyester resins prepared in examples 1 to 6 of the present invention have good mechanical properties.
Test example 2
The polyester resins prepared in examples 1 to 10 of the present invention and comparative examples 1 to 10 were uniformly coated after being stirred and mixed, and then cured, and were subjected to a comprehensive performance test.
The adhesion is determined according to GB/T1720-2020 paint film circle test;
the pencil hardness of the coating film is measured according to GB/T6739-2006 paint film hardness measured by a colored paint and varnish pencil method;
flexibility is measured according to GB/T1731-2020 paint film, putty film flexibility measuring method;
solvent resistance tests were performed according to astm d5402-06 using absolute ethanol, acetone and toluene as solvents.
The results are shown in Table 2.
TABLE 2
As is clear from the above table, the polyester resins prepared in examples 1 to 6 of the present invention have good combination of properties.
Test example 3
The polyester resins prepared in examples 1 to 10 and comparative examples 1 to 10 of the present invention were subjected to flame retardant property measurement and salt spray resistance test.
Salt spray resistance: the neutral salt fog resistance of the coating is tested by referring to GB/T1771-2007, the mass fraction of NaCl solution is 5%, the temperature is 35 ℃, the salt fog settlement is 1.5 mL/h, the test is 1000h, and if the bubbling or rust width of the coating exceeds 2mm, the coating does not pass.
Oxygen index was measured according to GB/T2406.2-2009 standard and vertical burn rating was measured according to GB/T2408-2021 standard. The spline size was 80 mm ×10 mm ×1mm.
The results are shown in Table 3.
TABLE 3 Table 3
As shown in the table above, the polyester resins prepared in examples 1 to 6 of the present invention have good flame retardant and salt spray corrosion resistance.
Test example 4
The polyester resins prepared in examples 1 to 10 and comparative examples 1 to 10 of the present invention were subjected to recycling processing after curing.
The specific method comprises the following steps: grinding the cured sample into powder, placing the powder on a flat vulcanization hot press for hot pressing at 210 ℃ for 2 hours to obtain a reprocessed sample, carrying out mechanical strength test on the reprocessed sample, and calculating the tensile strength and the elongation at break of the reprocessed sample to be the percentages of the initial sample respectively.
The mechanical properties were measured using a universal tensile tester with a load of 5 kN. The test conditions were 25℃and the stretching rate was 5mm/min, and the spline dimensions were 80 mm X10 mm X1 mm.
Tensile strength ratio (%) = tensile strength of reprocessed sample/tensile strength of initial sample x 100%
Elongation at break ratio (%) = elongation at break of reprocessed sample/elongation at break of initial sample x 100%
The results are shown in Table 4.
TABLE 4 Table 4
As can be seen from the above table, the polyester materials prepared in examples 1 to 6 of the present invention have a high strength and elongation and a high application value, although the mechanical properties of the recycled reprocessed samples are reduced.
Examples 7 and 8 were compared with example 3, in which no maleic acid or itaconic acid was added. Comparative example 3 in comparison with example 3, itaconic acid and maleic acid were not added. In examples 9 and 10, no maleic acid or itaconic acid was added as compared with example 6. Comparative example 8 in comparison with example 6, no itaconic acid and maleic acid were added. The mechanical property and the solvent resistance are reduced, the hardness is reduced, the flexibility is reduced, and the regeneration performance is reduced. The itaconic acid can be prepared by fermenting agriculture and forestry biomass such as lignocellulose through microorganisms, has wide raw material sources and low cost, contains conjugated double bonds and carboxyl groups in the molecule, has very active chemical properties, can be used as one of the reaction raw materials of the polyester resin, and has low viscosity and low volatility, so that the preparation process of the polyester resin is simpler and more convenient. In addition, the maleic acid is also a bio-based source diacid, and by introducing itaconic acid and maleic acid as the diacid, the mechanical property, solvent resistance and thermal stability of the polyester resin are obviously improved, the synergistic effect is achieved, the preparation cost is lower, and the bio-recycling can be realized.
Comparative example 1 compared to example 3, no flame retardant acid was added, or comparative example 6 compared to example 6, no flame retardant alcohol was added. The flame retardant property and the mechanical property are reduced. The 9, 10-diammine-9-oxa-10- phenanthrene-10-oxide (DOPO) and derivatives thereof have higher thermal stability, and can be used for preparing a reactive flame retardant, so that the flame retardant and the heat resistance of the polyester resin are improved by adding the reactive flame retardant into the synthesis of the polyester resin. According to the invention, the DOPO is reacted with the bio-based material itaconic acid to prepare the flame-retardant acid, so that the phosphorus content in the polyester resin is improved in the molecular formation of the polyester resin, the flame-retardant modified and heat-resistant modified effects are good, and the mechanical properties of the polyester resin are improved in the presence of the itaconic acid. In addition, the DOPO and the alkene glycol react to obtain a plurality of flame-retardant alcohols, the structure of the polyester resin is enriched, and the prepared polyester resin has good flame retardance and heat resistance. The preparation method of the flame-retardant acid and the flame-retardant alcohol is simple, the yield is high, and the synthesis conditions are mild.
Comparative example 2 did not add 3,3 '-dithiobis (propan-1-ol) as compared to example 3, or comparative example 7 did not add 3,3' -dithiodipropionic acid as compared to example 6. The regeneration performance is significantly reduced. According to the invention, the disulfide diol and the disulfide dicarboxylic acid are introduced, so that the disulfide compound can be used as a reaction raw material of the polyester resin, on the other hand, disulfide bonds of the disulfide compound have reversible covalent bonds, and the disulfide bonds can be broken and recombined when the disulfide compound is stimulated by the outside, so that the prepared polyester resin has the performances of repeated processing, recycling and the like, the environment friendliness of the polyester resin is greatly improved, the material is placed in a hot organic solution for soaking, the material can be completely dissolved, the recycling of the material is realized, meanwhile, the disulfide bond can be uniformly decomposed under the irradiation of common lamplight, and the repair of cracks of the polyester resin material is realized.
Comparative example 4 compared to example 3 or comparative example 9 compared to example 6, KH560 was not added in step S2. Comparative example 5 compared to example 3 or comparative example 10 compared to example 6, no modified silica sol was added in step S3. The mechanical properties are reduced, the salt spray corrosion resistance is reduced, the solvent resistance is reduced, the hardness is reduced, the flame retardant property is reduced, and the flexibility is reduced. In the preparation process of the polyester resin, KH560 modified silica particles are also added, and the modified silica particles are introduced, so that epoxy groups carried by the modified silica particles can participate in the synthesis of the resin due to the modification of KH560, so that inorganic particles are uniformly dispersed in the polyester resin, the dispersibility of inorganic materials is improved, and the mechanical property, high temperature resistance, corrosion resistance and ageing resistance of the polyester resin are greatly improved through the modification of the KH560 modified silica particles.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. A polyester resin is characterized in that the polyester resin is formed by dibasic acid, flame-retardant acid and/or flame-retardant alcohol, dithioglycol and/or dithiodicarboxylic acid and glycol components, and modified nano silicon dioxide is added;
the structural formula of the flame retardant acid is shown as formula I:
a formula I;
the structural formula of the flame-retardant alcohol is shown as formula II:
a formula II;
wherein r=c0-C3 alkyl chain;
the modified nano silicon dioxide is KH560 modified nano silicon dioxide particles;
the dibasic acid is a mixture of itaconic acid and maleic acid, and the molar ratio is 10-12:3-5; the dithioglycol is at least one selected from 3,3 '-dithiobis (propane-1-ol) and 3,3' -dithiobis (hexane-1-ol); the dithiodicarboxylic acid is 3,3' -dithiodipropionic acid; the dihydric alcohol is at least one selected from ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol and neopentyl glycol.
2. The polyester resin according to claim 1, wherein the polyester resin is formed of itaconic acid, maleic acid, flame retardant acid, 3' -dithiobis (propan-1-ol), 1, 2-propanediol component in a molar ratio of 10-12:3-5:0.5-1:1-2:11.5-16.
3. The polyester resin according to claim 1, which is formed of itaconic acid, maleic acid, flame retardant alcohol, 3' -dithiodipropionic acid, and ethylene glycol components in a molar ratio of 10-12:3-5:0.7-1.2:0.9-1.5:13.2-17.3.
4. The polyester resin according to claim 1, wherein the method for preparing the flame retardant acid comprises the following steps: dissolving 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid in a solvent, heating and stirring for reaction under the protection of inert gas, filtering, washing and drying to obtain the flame-retardant acid.
5. The polyester resin according to claim 4, wherein the molar ratio of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to itaconic acid is 1:1-1.05, the solvent is at least one of toluene, xylene and tetrahydrofuran, the temperature of the heating and stirring reaction is 100-110 ℃ and the time is 7-10h.
6. The polyester resin according to claim 1, wherein the flame-retardant alcohol is prepared by the following method: dissolving 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dihydric alcohol in a solvent, heating and stirring for reaction under the protection of inert gas, filtering, washing and drying to obtain the flame-retardant alcohol.
7. The polyester resin according to claim 6, wherein the molar ratio of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the glycol is 1:1.1-1.2, the glycol is at least one selected from the group consisting of 1-ethylene-1, 2-diol, 2-butene-1, 4-diol, 3-hexene-1, 6-diol and 4-octene-1, 8-diol, the solvent is at least one selected from toluene, xylene, tetrahydrofuran and ethyl acetate, and the temperature of the heating and stirring reaction is 90-100 ℃ for 6-8 hours.
8. A method for producing the polyester resin according to any one of claims 1 to 7, comprising the steps of:
s1, uniformly mixing dibasic acid, flame-retardant acid and/or flame-retardant alcohol, dithioglycol and/or dithiodicarboxylic acid, dihydric alcohol, polymerization inhibitor and catalyst, heating and stirring for reaction, stopping heating when the acid value is reduced to 45-50mgKOH/g, cooling to room temperature, adding dichloromethane for dissolution, standing, and removing the solvent under reduced pressure to obtain a prepolymer;
s2, adding the alkyl orthosilicate into ethanol, adding KH560, water and ammonia water, heating, stirring and mixing for reaction to form sol, and obtaining modified silica sol;
s3, adding the prepolymer prepared in the step S1 and the modified silica sol prepared in the step S2 into a diluent, adding an initiator, stirring and mixing uniformly, and reacting and curing to obtain the polyester resin.
9. The preparation method of claim 8, wherein the polymerization inhibitor is hydroquinone, the addition amount is 0.5-1wt% of the total mass of the system, the catalyst is p-toluenesulfonic acid or cobalt isooctanoate, the addition amount is 0.01-0.02wt% of the total mass of the system, the initiator is 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide or methyl ethyl ketone peroxide, the mass ratio of the modified silica sol, the prepolymer, the diluent and the initiator is 3-5:15-20:10-20:0.01-0.02, the curing condition is ultraviolet light curing for 10-15min or heating to 50-60 ℃ for curing for 1-2h, the mass ratio of the alkyl orthosilicate, ethanol, KH560, water and ammonia water is 12-15:30-50:3-5:15-20:7-10, the concentration of the ammonia water is 22-25wt%, and the alkyl orthosilicate is methyl orthosilicate or ethyl orthosilicate.
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| CN101389687A (en) * | 2006-01-20 | 2009-03-18 | 通用电气公司 | A process for making polyesters |
| CN115725229A (en) * | 2021-12-06 | 2023-03-03 | 烟台大学 | Self-repairing flame-retardant, molten drop-resistant and abrasion-resistant polyurethane coating material |
| CN116239763A (en) * | 2023-03-23 | 2023-06-09 | 烟台中科先进材料与绿色化工产业技术研究院 | Preparation method and application of flame-retardant polyester polyol containing DOPO and preparation method of flame-retardant polyurethane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101389687A (en) * | 2006-01-20 | 2009-03-18 | 通用电气公司 | A process for making polyesters |
| CN115725229A (en) * | 2021-12-06 | 2023-03-03 | 烟台大学 | Self-repairing flame-retardant, molten drop-resistant and abrasion-resistant polyurethane coating material |
| CN116239763A (en) * | 2023-03-23 | 2023-06-09 | 烟台中科先进材料与绿色化工产业技术研究院 | Preparation method and application of flame-retardant polyester polyol containing DOPO and preparation method of flame-retardant polyurethane |
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